Vinyl ethers are extremely reactive monomers which are known to undergo polymerization by a cationic mechanism readily induced by ultraviolet or electron beam radiation and which are useful in applications which require high speed curing. Vinyl ethers undergo cationic curing much faster than the epoxy resins and therefore may be used for printing inks, coatings, elastomers, foams, and other types of materials dependent upon the ability of the formulation to cure at a rate which is consistent with other processing steps. A disadvantage attending the use of vinyl ethers is their relatively limited commercial availability. In general, the available vinyl ethers are low molecular weight monofunctional or difunctional monomers, whereas in most commercial applications higher molecular weight oligomeric materials are preferred for their lower volatility and more desirable rheological properties.
The present invention discloses vinyl ether terminated esters and urethanes from bis(hydroxyalkyl)cycloalkanes. As will be seen, the structure of such materials is susceptible to wide variations with a minimum change in the reactants. This flexibility permits facile variation in the properties and characteristics of the materials of our invention as well as comparable variations in the resulting cured polymers. Where the oligomer contains more than one vinyl ether group the cured materials are extensively cross-linked, very high molecular weight polymers. The polymers have a wide range of properties depending upon the structure of the oligomeric precursor. Although the vinyl ether terminated esters and urethanes of this invention have been designed to fill the need for radiation curable coatings, they may have a much broader use. In particular, the materials of our invention are readily polymerized by means other than radiation curing, and the resulting polymers are meant to be subsumed in our invention. What appears unique to the materials of our invention, and to bis(hydroxyalkyl)cycloalkanes as diols used in their preparation, is that coatings based on our materials give greatly improved adhesion to metal substrates. Adhesion to metals has been a weak performance area for radiation cured coatings generally. (UV and EB Curing Formulations for Printing Inks, Coatings, and Paints, "R. Holman Ed. Selective Industrial Training Associates, London (1984, p. 147)).